CN1240821A - Detergent builder, production process therefor, and poly-(meth) acrylic acid (or salt) polymer and use thereof - Google Patents

Abstract

The present invention provides a detergent builder and a production process therefor, which detergent builder comprises a polymer that has a narrow molecular weight distribution and is excellent both in the gelation resistance and the chelating ability. To produce this detergent builder, the ratio by weight of total amount of monomer component, chain transfer agent, and polymerization initiator to total amount of aqueous medium is set in the range of 46:54~66:34, and 10% or more of the aqueous medium and 0~50% (preferably 1~50%) of the chain transfer agent are beforehand charged into a reactor, and the polymerization is carried out at a reaction temperature of 50~120 DEG C. while 70% or more of the monomer component, and 80% or more of the polymerization initiator are gradually supplied to the reaction system.

Description

Detergent builder, its preparation method and poly-(methyl) vinylformic acid (or salt) polymkeric substance and uses thereof

The present invention relates to detergent builder, its preparation method and poly-(methyl) vinylformic acid (or salt) polymkeric substance and uses thereof.

Poly-(methyl) vinylformic acid (or salt) polymkeric substance is a kind of versatile polymkeric substance, for example as the dispersion agent of detergent builder, Scale inhibitors and mineral dye.Its typical preparation method comprises most of component is carried out step of polymerization for the monomer component of (methyl) vinylformic acid (or salt) in the presence of chain-transfer agent and polymerization starter in aqueous medium.

USP 2,789,099 discloses a kind of preparation method of acrylic acid polymer, it comprises carries out the step of polyreaction with a kind of aqueous solution that contains vinylformic acid, superoxide (polymerization starter) and a kind of special copper compound and a kind of special alkalt metal hypophophite (chain-transfer agent), and has provided an embodiment (compound experiment embodiment) of preferred embodiment.The disposable adding of all raw materials in this embodiment, polymerization is carried out in heating then.At first other all raw materials except that superoxide are added and heating in another embodiment, when polyreaction is carried out, add superoxide then again.This patent has been enumerated the purposes of acrylic acid polymer as fiber gluing agent, soil stabilizer, tackiness agent and emulsifying agent.

JP-A-011092/1980 discloses the purposes of a kind of special poly-(methyl) acrylate copolymer (telomer compound) as aqueous solution treatment agent, and provided the embodiment (compound experiment embodiment) of preferred embodiment, wherein the telomer compound be a kind of comprise sodium persulfate aqueous solution and vinylformic acid is added drop-wise in the sodium hypophosphite aqueous solution and in the method with the blend heated step of gained prepare.

JP-A-293599/1986 relates to a kind of thermotolerance Scale inhibitors that contains poly-(methyl) acrylate copolymer, and has provided an embodiment (compound experiment embodiment) of preferred embodiment.In this embodiment, water is added in the reactor and postheating, then when polyreaction is carried out to wherein the dropwise addition of acrylic acid aqueous solution, Hypophosporous Acid, 50 (or salt) aqueous solution and the polymerization starter aqueous solution.In another embodiment, at first Hypophosporous Acid, 50 solution is joined in the reactor and postheating, then when polyreaction is carried out to wherein dropwise addition of acrylic acid (aqueous solution) and initiators for polymerization (aqueous solution).

When poly-(methyl) vinylformic acid (or salt) polymkeric substance was used as detergent builder, mineral dye dispersion agent and Scale inhibitors, antigelation ability and sequestering power were its two performances that major requirement possesses.The antigelation ability represents that the polyvalent metal ion that exists in its opposing system such as calcium ion precipitate the index with the agglomerative phenomenon owing to contacting with poly-(methyl) vinylformic acid (or salt), it has been generally acknowledged that molecular weight is high more, and the antigelation ability is low more.Sequestering power is then represented the polyvalent metal ion that exists in it and the system such as the sequestering power of calcium ion, it has been generally acknowledged that molecular weight is high more, and sequestering power is strong more.Therefore consider to have equilibrium relationship between antigelation ability and the sequestering power from the molecular weight factor, it is difficult will reaching good antigelation ability and sequestering power simultaneously.

In addition, any poly-(methyl) vinylformic acid (or salt) for preparing according to the aforementioned described method of existing technology document all has very wide molecular weight distribution, promptly contain the high molecular and the low-molecular-weight component that depart from molecular-weight average greatly, these components can cause low antigelation ability and low sequestering power respectively.

A target of the present invention provides the preparation method of a kind of detergent builder and it, and these detergent builder contain poly-(methyl) vinylformic acid (or salt) polymkeric substance of all good narrow molecular weight distributions of antigelation ability and sequestering power.In addition, another target of the present invention provides poly-(methyl) vinylformic acid (or salt) polymkeric substance of narrow molecular weight distributions, it has good antigelation ability and sequestering power simultaneously, not only can be used as detergent builder expediently, and can be used as mineral dye dispersion agent and Scale inhibitors.

For addressing the above problem, the invention provides:

(1) a kind of washing composition that contains poly-(methyl) vinylformic acid (or salt) polymkeric substance helps

Agent, and the product of its antigelation ability (A) and sequestering power (B) (A * B)

More than or equal to 18000.

(2) preparation method of these detergent builder comprises most of component is (methyl)

Monomer component the depositing of vinylformic acid (or salt) at chain-transfer agent and polymerization starter

Descend step of polymerization in aqueous medium, obtaining containing the poly-(first of gained thus

Base) detergent builder of vinylformic acid (or salt) polymkeric substance;

The method is characterized in that:

Monomer component, chain-transfer agent and polymerization starter three's gross weight and water

The ratio of the gross weight of property medium is 46: 54 to 66: 34;

More than or equal to the aqueous medium of 10% (weight) of aqueous medium total amount and

The chain-transfer agent of 0～50% (weight) of chain-transfer agent total amount joins in advance

In the reactor; With

Polymerization is to carry out under 50～120 ℃ in temperature of reaction, in this process

In more than or equal to the monomer component of 70% (weight) of monomer component total amount, big

In the chain-transfer agent of 50% (weight) that equals the chain-transfer agent total amount and greater than etc.

Polymerization starter in 80% (weight) of polymerization starter total amount little by little adds

Go into and be 50～120 ℃ reaction system to temperature.

(2) poly-(methyl) vinylformic acid (or salt) polymkeric substance, it is by being included in greatly

The part component is that the monomer component of (methyl) vinylformic acid (or salt) is in chain transfer

Under the existence of agent and polymerization starter in aqueous medium the method for step of polymerization

And preparation;

This polymkeric substance is characterised in that:

Monomer component, chain-transfer agent and polymerization starter three's gross weight and water

The ratio of the gross weight of property medium is 46: 54 to 66: 34;

More than or equal to the aqueous medium of 10% (weight) of aqueous medium total amount and

The chain-transfer agent of 1～50% (weight) of chain-transfer agent total amount joins in advance

In the reactor; With

Polymerization is to carry out under 50～120 ℃ in temperature of reaction, in this process

In more than or equal to the monomer component of 70% (weight) of monomer component total amount, big

In the chain-transfer agent of 50% (weight) that equals the chain-transfer agent total amount and greater than etc.

The polymerization starter that draws 80% (weight) of mixture total amount in polymerization little by little adds

Go into and be 50～120 ℃ reaction system to temperature.

Above-mentioned target of the present invention and other target and its advantage will obtain complete explanation by following detailed disclosed content.

The contriver has studied and has obtained having more each preparation condition of poly-(methyl) vinylformic acid (or salt) polymkeric substance of narrow molecular weight distributions than common identical polymkeric substance.Found that: at first, the feed way of the raw material that polymerization is adopted (monomer component, chain-transfer agent, polymerization starter and aqueous medium), a kind of is that raw material joins in the reactor in advance, another kind is that raw material added gradually after reactive system was heated, preferred aqueous medium at first adds in raw material, and monomer component, chain-transfer agent and polymerization starter add after being heated gradually; For chain-transfer agent, preferably at first certain part adds in the reactor with it, and then adds rest parts gradually further.Secondly, the contriver has studied the ratio between these raw materials, found that different with conventional proportional range, the proportional range of the total amount of monomer component, chain-transfer agent and polymerization starter and the best of the total amount of aqueous medium existence.In addition, the contriver has studied the influence as factors such as temperature of reaction in great detail, and has finally finished target of the present invention.

Below present invention is described in detail.

The monomer component that the present invention adopts comprises that (methyl) vinylformic acid (or salt) is as its main ingredient.The implication of main ingredient is that 50% (weight) or more monomer component are (methyl) vinylformic acid (or salt).This ratio is preferably greater than and equals 60% (weight), more preferably greater than equaling 90% (weight), and 100% (weight) particularly.The increase of (methyl) vinylformic acid (or salt) ratio can obtain the polymkeric substance of high sequestering power in monomer component.The example of (methyl) vinylformic acid (or salt) comprising: vinylformic acid (or salt) monomer, for example vinylformic acid, monovalence metal acrylate salt (as sodium acrylate, potassium acrylate), ammonium acrylate and divalent metal acrylate (as vinylformic acid magnesium, calcium acrylate); Methacrylic acid (or salt) monomer, for example methacrylic acid, monovalence metal methacrylate (as sodium methacrylate, methacrylic acid potassium), ammonium methacrylate and divalent metal methacrylate (as magnesinm methacrylate, methacrylic acid calcium).These monomers can use separately or be used in combination each other respectively.In above-mentioned example, preferred vinylformic acid (or salt) monomer, particularly vinylformic acid.

In the present invention, monomer component also can comprise other and the above-mentioned copolymerizable monomer of (methyl) vinylformic acid (or salt) monomer, as long as they do not destroy effect of the present invention.Other monomeric example comprises: unsaturated monoprotic acid monomer, as Ba Dousuan; With above-mentioned unsaturated monoprotic acid monomer segment or the neutralized reaction product after neutralizing fully, the product that obtains with monovalence metal, divalent metal, ammonium or organic amine neutralization for example; Unsaturated dicarboxylic acid monomer is as toxilic acid, fumaric acid, methylene-succinic acid and citraconic acid; Neutralized reaction product after above-mentioned unsaturated dicarboxylic acid monomer partially or completely neutralized, for example product that obtains with monovalence metal, divalent metal, ammonium or organic amine neutralization; Amide monomer is as (methyl) acrylamide and the tertiary butyl (methyl) acrylamide; Hydrophobic monomer is as (methyl) acrylate, vinylbenzene, 2-methyl styrene and vinyl acetate; The unsaturated sulfonic acid monomer is as vinyl sulfonic acid, allyl sulphonic acid, methallylsulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, (methyl) vinylformic acid sulphur ethyl ester, (methyl) vinylformic acid sulphur propyl ester, (methyl) vinylformic acid 2-hydroxyl sulphur propyl ester and sulfoethyl maleimide; With above-mentioned unsaturated sulfonic acid monomer segment or the neutralized reaction product after neutralizing fully, the product that obtains with monovalence metal, divalent metal, ammonium or organic amine neutralization for example; The unsaturated monomer of hydroxyl, as 3-methyl-2-butene-1-alcohol, 3-methyl-3-butene-1-alcohol (prenol), 2-methyl-3-butene-2-alcohol (isoprene alcohol, isoprene alcohol), (methyl) vinylformic acid 2-hydroxy methacrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyethyleneglycol isopentene group ether, polypropylene glycol list isopentene group ether, the polyoxyethylene glycol mono allyl ether, the polypropylene glycol mono allyl ether, allylin, Alpha-hydroxy vinylformic acid, N-methylol (methyl) acrylamide, glycerine list (methyl) acrylate and vinyl alcohol; Cationic monomer is as (methyl) dimethylaminoethyl acrylate and (methyl) vinylformic acid dimethylamino propyl ester; Nitrile monomer is as (methyl) vinyl cyanide; Phosphorous-containing monomers is as (methyl) acrylamido methanephosphonic acid, (methyl) acrylamido methanephosphonic acid methyl esters and 2-(methyl) acrylamido-2-methylpropane phosphonic acids.These monomers can use separately respectively, also can be used in combination each other.The consumption of these monomers in monomer component be usually smaller or equal to 50% (weight), preferably smaller or equal to 40% (weight), is more preferably less than and equals 10% (weight), particularly 0% (weight).

Additional disclosure be that " monomer component " is meant above-mentioned various monomer components in principle in the present invention.But for example when adopting acid of 1 mol propylene and 1 molar sodium hydroxide, have 1 mol propylene acid sodium to generate by neutralization, at this moment sodium acrylate just is called as monomer component.In addition, when adopting acid of 1 mol propylene and 0.5 molar sodium hydroxide, what obtain by neutralization is the mixture of acid of 0.5 mol propylene and the sour sodium of 0.5 mol propylene, and at this moment this mixture just is called as the formation monomer component.

The object lesson of the polymerization starter that is adopted comprises in the present invention: hydrogen peroxide; Persulphate is as ammonium persulphate, Sodium Persulfate and Potassium Persulphate; Azo-compound, as 2,2 '-azo two (2-amidine propane) dihydrochloride, 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-Diisopropyl azodicarboxylate and 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile); Organo-peroxide is as benzoyl peroxide, lauroyl peroxide, peracetic acid, mistake Succinic Acid, ditertiary butyl peroxide, tertbutyl peroxide and isopropyl benzene hydroperoxide; But have no particular limits.These polymerization starters can use separately respectively, also can be used in combination each other.Wherein, especially preferably use persulphate.Polymerization starter has no particular limits with respect to the consumption of monomer component, but adopts 0.0001～0.05 mole of initiator comparatively suitable with 1 mole of monomer component.Incidentally, polyreaction can obtain promotion as sulfurous acid (hydrogen) salt or transition metal salt by adopting reductive agent with above-mentioned polymerization starter acting in conjunction.

The object lesson of chain-transfer agent of the present invention comprises: sulfocompound, as thioglycolic acid, thioacetic acid and mercaptoethanol; Phosphorons acid compound is as phosphorous acid and sodium phosphite; The Hypophosporous Acid, 50 compound is as Hypophosporous Acid, 50 and sodium hypophosphite; Alcohol compound is as methyl alcohol, ethanol, Virahol and butanols; But have no particular limits.These chain-transfer agents can use separately respectively, also can be used in combination each other.In above-mentioned concrete example, preferred Hypophosporous Acid, 50 compound, particularly sodium hypophosphite.Chain-transfer agent has no particular limits with respect to the consumption of monomer component, but adopts 0.005～0.15 mole of chain-transfer agent comparatively suitable with 1 mole of monomer component.

The example of aqueous medium of the present invention comprises: water; The mixing solutions of water and water-soluble solvent.The example of water-soluble solvent comprises: lower alcohol, as methyl alcohol, ethanol, Virahol and butanols; Lower ketones is as acetone and butanone; Rudimentary ether is as dme and methyl ethyl ether.The content of water is preferably more than and equals 40% (weight) in the mixing solutions, but especially preferably only adopts water as medium.Incidentally, about " aqueous medium " of the present invention, the prerequisite of its calculating is beyond demonomerization component, chain-transfer agent and the polymerization starter, and all components soluble in water all be included in the aqueous medium.For example, when 1 molar sodium hydroxide is adopted in per 0.5 mol propylene acid, there is 0.5 mole of water to generate, remains 0.5 mole sodium hydroxide by neutralization.This sodium hydroxide of 0.5 mole is still soluble in water so just should be included in this sodium hydroxide of 0.5 mole in the aqueous medium when calculating.In addition, the prerequisite of calculating is that the water that generates as vinylformic acid and sodium hydroxide neutralization or the like is also included within " aqueous medium ".Incidentally, when adopting the hydration sodium hypophosphite as chain-transfer agent, the water of hydration that calculating should be considered in the chain-transfer agent to be comprised.

The ratio of the gross weight of monomer component, chain-transfer agent and polymerization starter three's gross weight and aqueous medium should be 46: 54 to 66: 34 in the present invention, is preferably 48: 52 to 64: 36, particularly 50: 50 to 60: 40.Ratio less than 46: 54 situation under, can not get big product (polymkeric substance of the present invention of A * B), and the polymkeric substance that can not get having narrow molecular weight distributions of antigelation ability (A) and sequestering power (B).Ratio greater than 66: 34 situation under, preparation efficiency may reduce, and has reduced preparation efficiency such as needing owing to polymerization time to prolong.

In the present invention, need join in the reactor in advance, and this ratio preferably is at least 15% (weight), particularly at least 20% (weight) more than or equal to the aqueous medium of 10% (weight) of aqueous medium total amount.In other words, permission does not join in the reactor in advance smaller or equal to the aqueous medium of 90% (weight) of aqueous medium total amount, but joins in the reaction system gradually subsequently.Be mainly used in the water of dissolved monomer component, chain-transfer agent and polymerization starter, add gradually corresponding to the aqueous medium main body of aqueous medium (promptly as).When the amount that joins the aqueous medium in the reactor in advance during, the polymkeric substance of narrow molecular weight distributions will be can not get having less than 10% (weight).

In addition, more than or equal to the monomer component of 70% (weight) of monomer component total amount with need to join temperature gradually more than or equal to the polymerization starter of 80% (weight) of polymerization starter total amount be in 50～120 ℃ the reaction system, and this ratio is preferably more than the polymerization starter of 90% (weight) of the monomer component of 85% (weight) that equals the monomer component total amount and polymerization starter total amount, particularly more than or equal to the polymerization starter of 95% (weight) of the monomer component of 90% (weight) of monomer component total amount and polymerization starter total amount.In other words, can join in the reactor in advance smaller or equal to the monomer component of 30% (weight) of monomer component total amount with smaller or equal to the polymerization starter of 20% (weight) of polymerization starter total amount.When the amount of the monomer component that adds gradually, will can not get having the polymkeric substance of narrow molecular weight distributions, and needs to adopt a large amount of polymerization starters during less than 80% (weight) less than the amount of 70% (weight) or the polymerization starter that adds gradually.

Further, for chain-transfer agent, when the polymkeric substance of gained is used as detergent builder, the chain-transfer agent of 0～50% (preferred 1～50%) (weight) of chain-transfer agent total amount need join in advance in the reactor and need join temperature gradually more than or equal to the chain-transfer agent of 50% (preferred 50～99%) (weight) of chain-transfer agent total amount is in 50～120 ℃ the reaction system.In addition, when the polymkeric substance of gained during as the purposes beyond the detergent builder (as mineral dye dispersion agent and Scale inhibitors), the chain-transfer agent of 1～50% (weight) of chain-transfer agent total amount need join in the reactor in advance and the chain-transfer agent of 50～99% (weight) of chain-transfer agent total amount needs to add gradually.When the amount of the chain-transfer agent that adds gradually during, will can not get having the polymkeric substance of narrow molecular weight distributions, and need to adopt a large amount of chain-transfer agents less than 50% (weight).In addition, compare with the situation that all chain-transfer agents add gradually, as the fruit part chain-transfer agent (smaller or equal to 50% (weight), or when polymkeric substance during as the purposes beyond the detergent builder, 1～50% (weight)) join in the reactor in advance, the molecular weight distribution of resulting polymers can be narrower, and can more save the consumption of chain-transfer agent.No matter be that polymkeric substance is used as detergent builder or as other purposes, for chain-transfer agent, preference chain transfer agent total amount 5～45%, particularly the chain-transfer agent of 10～30% (weight) of chain-transfer agent total amount join in the reactor in advance and the chain-transfer agent total amount 55～95%, particularly the chain-transfer agent of 70～90% (weight) of chain-transfer agent total amount adds subsequently gradually.

In the present invention, the implication that adds raw material (monomer component, chain-transfer agent, polymerization starter and aqueous medium) in reactor in advance is before the reaction system heating raw material to be joined in the reactor.On the other hand, raw material adds fashionable temperature range gradually, and to be 50～120 ℃ be important, and this temperature range is preferably 60～115 ℃, particularly 90～110 ℃.Be lower than in temperature under 50 ℃ the situation, the molecular weight of generation is just too high, and the antigelation ability descends greatly.Be higher than in temperature under 120 ℃ the situation, the molecular weight of generation is just low excessively, can not get having the polymkeric substance of high sequestering power.The mode that adds raw material in reaction system gradually can be that continuous processing is reinforced or interrupter method is reinforced.

Poly-(methyl) vinylformic acid (or salt) polymkeric substance that obtains when final hope is when gathering (methyl) acrylate, adopt main ingredient to carry out polymerization for (methyl) acrylic acid monomer component, and after polymerization, the polymkeric substance of gained is neutralized with alkaline reagents (as sodium hydroxide), this method (being called as " acid type " method) is more better than adopting (methyl) acrylate to carry out polymeric method (being called as " salt type " method) as monomer component, because the acid type method has narrower molecular weight distribution than the polymkeric substance that salt type method obtains.

Poly-(methyl) vinylformic acid (or salt) polymkeric substance of the present invention, the product of its antigelation ability (A) and sequestering power (B) (A *, be preferably 30000～250000, particularly 70000～200000 B) more than or equal to 18000.Grasp that long-pending (A * B) then shows the deficiency on the performance, the deficiency of use properties during for example as detergent builder, mineral dye dispersion agent and Scale inhibitors less than poly-(methyl) vinylformic acid (or salt) polymkeric substance of 18000.(numerical value of A * B) is high more, and the use properties of polymkeric substance during for example as detergent builder, mineral dye dispersion agent and Scale inhibitors is just good more for product.But (A * B) surpasses under the situation of 250000 polymkeric substance, and the formation efficiency of polymkeric substance is then for example because the prolongation of preparation time or become lower because polymerization temperature need carry out strict control attempting to prepare product.(A * B) is more than or equal to 18000 polymkeric substance can to prepare product according to aforesaid method of the present invention.When the desired above-mentioned all conditions of preparation method of the present invention is not satisfied, (A * B) is more than or equal to 18000 polymkeric substance, the polymkeric substance of desired enough functions when therefore also can not get having for example as detergent builder, mineral dye dispersion agent and Scale inhibitors will to can not get product.

As long as product (A * B) more than or equal to 18000, poly-(methyl) vinylformic acid (or salt) polymkeric substance antagonism gelling ability (A) of the present invention also has no special requirements, but antigelation ability (A) preferably is at least 70, and particularly 80.In addition, sequestering power (B) preferably is at least 150, and particularly at least 210.

Incidentally, antigelation ability (A) and sequestering power (B) are measured according to the described testing method of this specification sheets " preferred embodiment detailed description ".Antigelation ability (A) does not have unit, and the unit of sequestering power (B) is (milligram CaCO ₃/ gram, mgCaCO ₃/ g).

Poly-(methyl) vinylformic acid (or salt) polymkeric substance of the present invention has narrow molecular weight distribution, and the scope that is defined as the molecular weight distribution of weight-average molecular weight/number-average molecular weight is 1.5～2.8, is preferably 1.5～1.8.Molecular weight distribution surpasses 2.8 polymkeric substance, and its antigelation ability and sequestering power are relatively poor.Molecular weight distribution is lower than 1.5 polymkeric substance then needs long preparation time or strict temperature control, therefore possibly can't obtain this polymkeric substance under low cost.In advance will part (1～50% (weight)) chain-transfer agent in aforesaid preparation method joining and can easily preparing molecular weight distribution in the reactor is 1.5～1.8 polymkeric substance.Particularly when polymkeric substance during as other purposes (for example as mineral dye dispersion agent or Scale inhibitors) except that detergent builder, molecular weight distribution especially requires narrower.

The weight-average molecular weight of poly-(methyl) vinylformic acid (or salt) polymkeric substance is preferably 1000～100000, and particularly 2000～50000.Especially, if poly-(methyl) vinylformic acid (or salt) polymkeric substance is by containing more than or equal to the monomeric monomer component preparation of 90% (weight) (methyl) vinylformic acid (or salt), and the weight-average molecular weight of polymkeric substance is 1000～100000, and further, if poly-(methyl) vinylformic acid (or salt) polymkeric substance is by containing the monomeric monomer component preparation of 100% (weight) (methyl) vinylformic acid (or salt), and the weight-average molecular weight of polymkeric substance is 2000～50000, and (A * B) is more than or equal to poly-(methyl) vinylformic acid (or salt) polymkeric substance of 18000 so just to be easy to obtain product.

In addition, when poly-(methyl) vinylformic acid (or salt) polymkeric substance when the detergent builder, the weight-average molecular weight of polymkeric substance is preferably 2000～100000, particularly 3000～10000.When poly-(methyl) vinylformic acid (or salt) polymkeric substance when the mineral dye dispersion agent, the weight-average molecular weight of polymkeric substance is preferably 2000～50000, particularly 3000～30000.When poly-(methyl) vinylformic acid (or salt) polymkeric substance when the Scale inhibitors, the weight-average molecular weight of polymkeric substance is preferably 1000～30000, particularly 2000～10000.

In addition, as mentioned above, poly-in the present invention (methyl) vinylformic acid (or salt) polymkeric substance is preferably adopting the Hypophosporous Acid, 50 compound to be prepared as under the chain-transfer agent.In this case, the polymkeric substance of gained contains the phosphorus atom that is brought by the Hypophosporous Acid, 50 compound in its molecule.

Poly-(methyl) vinylformic acid (or salt) polymkeric substance of the present invention has identical purposes with common poly-(methyl) vinylformic acid (or salt) polymkeric substance, but particularly when being used as detergent builder, mineral dye dispersion agent and Scale inhibitors, the former has better effect.

Detergent builder of the present invention contain poly-(methyl) vinylformic acid (or salt) polymkeric substance of the invention described above.

Even poly-(methyl) vinylformic acid (or salt) is when polymkeric substance is used alone as detergent builder, detergent builder of the present invention also have higher effect.If but 1～1000 part (weight) poly-(methyl) vinylformic acid (or salt) polymkeric substance and 100 parts of (weight) inorganic assistant agents are when using jointly, the effect that shows is then big especially.The consumption of polymkeric substance is during less than 1 part (weight), and the cleaning function that shows is the same low when only adopting inorganic assistant agent basically.In addition, even the consumption of polymkeric substance surpasses 1000 parts (weight), also can't see and have higher effect.

The example that can be used for inorganic assistant agent of the present invention comprises zeolite and tripoly phosphate sodium STPP (STPP).

Mineral dye dispersion agent of the present invention contains poly-(methyl) vinylformic acid (or salt) polymkeric substance of the invention described above.

Even when poly-(methyl) vinylformic acid (or salt) polymkeric substance was used alone as the mineral dye dispersion agent, mineral dye dispersion agent of the present invention also had higher effect.But this mineral dye dispersion agent further also can contain other dispersion agent (for example organic dispersing agent, inorganic dispersant such as hexametaphosphate and pyrophosphate salt) as required.

Mineral dye dispersion agent of the present invention can be used for disperseing mineral dye, for example kaolin, clay, natural calcium, various lime carbonate (synthetic calcium carbonate), titanium dioxide, calcium sulfate, barium sulfate, stain white, red iron oxide, zinc white and aluminium hydroxide.

Scale inhibitors of the present invention contains poly-(methyl) vinylformic acid (or salt) polymkeric substance of the invention described above.

Even poly-(methyl) vinylformic acid (or salt) is when polymkeric substance is used alone as Scale inhibitors, Scale inhibitors of the present invention also has higher effect.But this Scale inhibitors also can contain other additive as required.

Scale inhibitors of the present invention can directly join in the aqueous systems of for example cold water system and boiling water system.Also contain at Scale inhibitors under the situation of other component except that above-mentioned polymkeric substance, the component of Scale inhibitors can add in the aqueous systems each other by oneself.

Scale inhibitors of the present invention can be used for preventing and removes various incrustation scales, for example lime carbonate, calcium phosphate, barium sulfate, calcium sulfate, calcium sulfite, Calucium Silicate powder, Magnesium Silicate q-agent, magnesium hydroxide, zinc hydroxide, zinc phosphate, zinc subcarbonate, silica and molysite.

The present invention can provide has narrow molecular weight distributions, and antigelation ability and all good poly-(methyl) vinylformic acid (or salt) polymkeric substance of sequestering power.The detergent builder, mineral dye dispersion agent and the Scale inhibitors that contain this poly-(methyl) vinylformic acid (or salt) polymkeric substance have excellent effect.

Embodiment (compound experiment embodiment) by following certain preferred embodiments compares with non-comparing embodiment of the present invention, and the present invention will obtain more specific description hereinafter.But the present invention is not subjected to the restriction of these embodiment.

In embodiment and comparing embodiment, unless otherwise indicated, " part " and " % " all by weight.

The measuring method of molecular weight, molecular weight distribution, antigelation ability (A) and sequestering power (B) is as follows in the present invention.

＜molecular weight and molecular weight distribution 〉

For poly-(methyl) vinylformic acid (or salt) polymkeric substance, its molecular weight and molecular weight distribution (D value) are measured with GPC.Condition determination is as follows:

Pump: L-7100 (manufacturing of Hitachi Seisakusho company limited);

Carrier fluid: ultrapure water is joined in 34.5 gram disodium hydrogen phosphate dodecahydrates and 46.2 grams, the two hypophosphite monohydrate sodium dihydrogens, and be adjusted to the aqueous solution that gross weight is 5000 gram back gained;

Flow velocity: 0.5 ml/min;

Post: a GF-7MHQ water-based GPC post (manufacturing of Showa Denko company);

Detector: UV-detector, wavelength 214 nanometers, L-7400 type (manufacturing of HitachiSeisakusho company limited);

Molecular weight standard sample: sodium polyacrylate (manufacturing of Sowa Kagaku company).

The measuring method of＜antigelation ability 〉

Preparation 1% poly-(methyl) sodium acrylate aqueous solution.Ultrapure water is joined in 7.42 gram boric acid, 1.75 gram sodium-chlor and 7.63 grams, ten hydrated sodium borates, and to regulate gross weight be 1000 grams, obtain the borate buffer aqueous solution.Ultrapure water is joined in 0.735 gram, the two hydration calcium chloride, and to regulate gross weight be 5000 grams, obtain calcium chloride water.

Then, 250 gram ultrapure waters, the above-mentioned borate buffer aqueous solution of 10 grams, the 250 above-mentioned calcium chloride waters of gram and 5 grams above-mentioned 1% poly-(methyl) sodium acrylate aqueous solution to be joined a volume be in 500 milliliters the beaker and fully mix.Cover beaker then, be placed in the automatic heat regulator (its internal temperature is adjusted to 90 ℃ in advance) and left standstill 1 hour.Immediately the aqueous solution of gained is poured out beaker, and to join a pond length be in 5 centimetres the quartz cell, to measure the absorbancy a of the aqueous solution under 380 nano wave lengths.

In addition, 500 gram ultrapure waters, the 10 above-mentioned borate buffer aqueous solution of gram and 5 grams above-mentioned 1% poly-(methyl) sodium acrylate aqueous solution to be joined a volume be in 500 milliliters the beaker and fully mix.Cover beaker then, be placed in the automatic heat regulator (its internal temperature is adjusted to 90 ℃ in advance) and left standstill 1 hour.Immediately the aqueous solution of gained being poured out beaker and joining a pond length is to measure the absorbancy b of the aqueous solution under 380 nano wave lengths in 5 centimetres the quartz cell.In other words, measure and not have the absorbancy b of calcium chloride water under existing as blank.

Then, calculate the antigelation ability according to equation by above-mentioned absorbancy a and absorbancy b:

Antigelation ability=1/ (absorbancy a-absorbancy b)

The measuring method of＜sequestering power 〉

It is in 100 milliliters the beaker that 50 grams, 0.001 mol calcium chloride water is joined volume, and to wherein adding 10 milligrams of poly-(methyl) acrylate.With dilute solution of sodium hydroxide the pH value of gained solution is adjusted to 9～11 then.Subsequently, under agitation be that the potassium chloride solution of 4 mol adds wherein as the calcium ion electrode stablizer with 1 ml concn.

With an ion analyzer (EA920 type, the manufacturing of OLION company) measures the free calcium ion, come the milligram number (sequestering power) of calcium ion of the calcium carbonate form of poly-(methyl) acrylate institute of the every gram of measuration chelating with calcium ion electrode (93-20 type, OLION company make).The unit of sequestering power is " milligram lime carbonate/gram " (" mgCaCO ₃/ g ").

The synthetic embodiment of poly-(methyl) vinylformic acid (or salt) polymkeric substance is embodiment A of face-1～10 and Comparative Example A An-1～7 as follows.Incidentally, for the embodiment A in the embodiment A-1～10-1,8 and 9,1～50% chain-transfer agent is joined in the reactor in advance, then remainder is added gradually, so resulting polymers is included among the compound experiment embodiment of the present invention as the purposes of detergent builder and other purposes.For the embodiment except that embodiment A-1,8 and 9 in the embodiment A series, 100% chain-transfer agent is added gradually, so resulting polymers is included among the compound experiment embodiment of the present invention as the purposes of detergent builder, but their other purposes then is not included in wherein.For the polymkeric substance of Comparative Example A An-1～7 gained, their purposes or other purposes as detergent builder all are not included among the synthetic embodiment of the present invention.

(embodiment A-1)

At first, joining a volume of being furnished with agitator and condenser with 805.5 parts through the water of ion exchange treatment and 40.1 part of 45% single hydration sodium hypophosphite aqueous solution is in 5 liters the separable flask of SUS316 type, and under agitation temperature is risen to the boiling temperature (100 ℃) of system subsequently.

Enter the mouth to wherein dripping following raw materials according respectively by different droppings: 2126.1 part of 80% acrylic acid aqueous solution (containing 1700.9 parts of vinylformic acid and 425.2 parts of water) through ion exchange treatment, 112.4 part 15% sodium persulfate aqueous solution (containing 16.86 parts of Sodium Persulfates and 95.54 parts of water) through ion exchange treatment, with 160.2 part of 45% single hydration sodium hypophosphite aqueous solution (containing 70.11 parts of single hydration sodium hypophosphites and 90.09 parts of water), wherein: 80% acrylic acid aqueous solution through ion exchange treatment, the dropping time of 15% sodium persulfate aqueous solution and 45% single hydration sodium hypophosphite aqueous solution was respectively 180 minutes, 185 minutes and 180 minutes; The consumption of Sodium Persulfate is 0.003 mole of per 1 mol propylene acid; Total consumption of single hydration sodium hypophosphite is 0.036 mole of per 1 mol propylene acid; The ratio of the total amount of monomer component, chain-transfer agent and polymerization starter and the total amount of aqueous medium is 56: 44; The amount of the aqueous medium in the initial adding reactor accounts for 58% of aqueous medium total amount; The amount of the single hydration sodium hypophosphite in the initial adding reactor accounts for 20% of single hydration sodium hypophosphite total amount; Remain on the boiling temperature (100～105 ℃) of system with temperature of reaction in the dropping process.

After drip finishing, with system temperature with preceding identical temperature under kept 5 minutes obtaining polyacrylic acid (1) thus so that reaction transforms fully.

For polyacrylic acid (1), measure its molecular weight and molecular weight distribution (D value) according to aforesaid method.The results are shown in Table 1 for it.

(embodiment A-2)

At first, 805.5 parts of water through ion exchange treatment are joined in the identical aggregation container that is adopted with embodiment A-1, and under agitation temperature is risen to the boiling temperature (100 ℃) of system subsequently.

Enter the mouth to wherein dripping following raw materials according respectively by different droppings: 2126.1 part of 80% acrylic acid aqueous solution (containing 1700.9 parts of vinylformic acid and 425.2 parts of water) through ion exchange treatment, 112.4 part 15% sodium persulfate aqueous solution (containing 16.86 parts of Sodium Persulfates and 95.54 parts of water) through ion exchange treatment, with 250.4 part of 45% single hydration sodium hypophosphite aqueous solution (containing 112.7 parts of single hydration sodium hypophosphites and 137.7 parts of water), wherein: 80% acrylic acid aqueous solution through ion exchange treatment, the dropping time of 15% sodium persulfate aqueous solution and 45% single hydration sodium hypophosphite aqueous solution was respectively 180 minutes, 185 minutes and 180 minutes; The consumption of Sodium Persulfate is 0.003 mole of per 1 mol propylene acid; Total consumption of single hydration sodium hypophosphite is 0.045 mole of per 1 mol propylene acid; The ratio of the total amount of monomer component, chain-transfer agent and polymerization starter and the total amount of aqueous medium is 56: 44; The amount of the aqueous medium in the initial adding reactor accounts for 55% of aqueous medium total amount; Remain on the boiling temperature (100～105 ℃) of system with temperature of reaction in the dropping process.

After drip finishing, with system temperature with preceding identical temperature under kept 5 minutes obtaining polyacrylic acid (2) thus so that reaction transforms fully.

For polyacrylic acid (2), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(embodiment A-3)

Prepare polyacrylic acid (3) according to the polyreaction identical, except replacing 805.5 parts of water with 1172 parts of water when reinforced through ion exchange treatment through ion exchange treatment initial with embodiment A-2.For polyacrylic acid (3), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(embodiment A-4)

Prepare polyacrylic acid (4) according to the polyreaction identical, except replacing 805.5 parts of water with 1405.6 parts of water when reinforced through ion exchange treatment through ion exchange treatment initial with embodiment A-2.For polyacrylic acid (4), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(embodiment A-5)

Prepare polyacrylic acid (5) according to the polyreaction identical, except replacing 805.5 parts of water with 305 parts of water when reinforced through ion exchange treatment through ion exchange treatment initial with embodiment A-2.For polyacrylic acid (5), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(embodiment A-6)

Prepare vinylformic acid/Sipacril 2739OF (6) according to the polyreaction identical, except being that vinylformic acid/methacrylic aqueous acid of 6/4 replaces 2126.1 part of 80% acrylic acid aqueous solution with 2126.1 part of 80% mol ratio with embodiment A-2.For vinylformic acid/Sipacril 2739OF (6), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(embodiment A-7)

At first, 482.6 parts of water through ion exchange treatment are joined in the identical aggregation container that is adopted with embodiment A-1, and under agitation temperature is risen to the boiling temperature (100 ℃) of system subsequently.

Enter the mouth to wherein dripping following raw materials according respectively by different droppings: 2126.1 part of 80% acrylic acid aqueous solution (containing 1700.9 parts of vinylformic acid and 425.2 parts of water) through ion exchange treatment, 112.4 part 15% sodium persulfate aqueous solution (containing 16.9 parts of Sodium Persulfates and 95.5 parts of water) through ion exchange treatment, 250.4 part 45% single hydration sodium hypophosphite aqueous solution (containing 112.7 parts of single hydration sodium hypophosphites and 137.7 parts of water) through ion exchange treatment, with 1870.2 part of 48% aqueous sodium hydroxide solution, wherein: 80% acrylic acid aqueous solution, 15% sodium persulfate aqueous solution, the dropping time of 45% single hydration sodium hypophosphite aqueous solution and 48% aqueous sodium hydroxide solution was respectively 180 minutes, 185 minutes, 180 minutes and 180 minutes; The consumption of Sodium Persulfate is 0.003 mole of per 1 mol propylene acid; Total consumption of single hydration sodium hypophosphite is 0.045 mole of per 1 mol propylene acid; The consumption of sodium hydroxide is 0.95 mole of per 1 mol propylene acid; The ratio of the total amount of monomer component, chain-transfer agent and polymerization starter and the total amount of aqueous medium is 48: 52; The amount of the aqueous medium in the initial adding reactor accounts for 19% of aqueous medium total amount; Remain on the boiling temperature (100～105 ℃) of system with temperature of reaction in the dropping process.

After drip finishing, with system temperature with preceding identical temperature under kept 5 minutes obtaining sodium polyacrylate (7) thus so that reaction transforms fully.For sodium polyacrylate (7), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(embodiment A-8)

Prepare polyacrylic acid (8) according to the polyreaction identical with embodiment A-1, except replacing 40.1 part of 45% single hydration sodium hypophosphite aqueous solution and when dripping, replace 160.2 part of 45% single hydration sodium hypophosphite aqueous solution with 10.0 part of 45% single hydration sodium hypophosphite aqueous solution when reinforced with 190.3 part of 45% single hydration sodium hypophosphite aqueous solution initial.For polyacrylic acid (8), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(embodiment A-9)

Prepare polyacrylic acid (9) according to the polyreaction identical with embodiment A-1, except replacing 40.1 part of 45% single hydration sodium hypophosphite aqueous solution and when dripping, replace 160.2 part of 45% single hydration sodium hypophosphite aqueous solution with 90.1 part of 45% single hydration sodium hypophosphite aqueous solution when reinforced with 110.2 part of 45% single hydration sodium hypophosphite aqueous solution initial.For polyacrylic acid (9), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(embodiment A-10)

Prepare polyacrylic acid (10) according to the polyreaction identical, except replacing 250.4 part of 45% single hydration sodium hypophosphite aqueous solution with 88.5 part of 45% single hydration sodium hypophosphite aqueous solution (containing 37.6 parts of single hydration sodium hypophosphites and 45.9 parts of water) through ion exchange treatment with embodiment A-2.For polyacrylic acid (10), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 1 for it.

(Comparative Example A An-1)

Prepare comparison polyacrylic acid (1) according to the polyreaction identical, except replacing 805.5 parts of water with 1671.2 parts of water when reinforced through ion exchange treatment through ion exchange treatment initial with embodiment A-2.For comparing polyacrylic acid (1), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 2 for it.

(Comparative Example A An-2)

Prepare comparison polyacrylic acid (2) according to the polyreaction identical with embodiment A-2, except 250.4 part of 45% single hydration sodium hypophosphite aqueous solution is not by dripping, but when initial, just join in the reactor, in other words, be used as the raw material of initial adding with 805.5 parts of mixtures through the water of ion exchange treatment and 250.4 part of 45% single hydration sodium hypophosphite aqueous solution.For comparing polyacrylic acid (2), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 2 for it.

(Comparative Example A An-3)

At first, with 805.5 parts of water through ion exchange treatment, 850.4 part 80% acrylic acid aqueous solution (account for monomer total amount 40%), 33.7 part 15% sodium persulfate aqueous solution (account for Sodium Persulfate total amount 30%) and 150.2 part of 45% single hydration sodium hypophosphite aqueous solution (account for single hydration sodium hypophosphite total amount 60%) join in the identical aggregation container that is adopted with embodiment A-1, and under agitation temperature are risen to lentamente the boiling temperature (103 ℃) of system subsequently.

By different dropping inlet to wherein dripping following raw materials according respectively: 1275.7 part of 80% acrylic acid aqueous solution (account for monomer total amount 60%), 78.7 part 15% sodium persulfate aqueous solution (account for Sodium Persulfate total amount 70%), with 100.1 part of 45% single hydration sodium hypophosphite aqueous solution (account for single hydration sodium hypophosphite total amount 40%), wherein: the dropping time of 80% acrylic acid aqueous solution, 15% sodium persulfate aqueous solution and 45% single hydration sodium hypophosphite aqueous solution was respectively 180 minutes, 185 minutes and 180 minutes; The consumption of Sodium Persulfate is 0.003 mole of per 1 mol propylene acid; Total consumption of single hydration sodium hypophosphite is 0.045 mole of per 1 mol propylene acid; The ratio of the total amount of monomer component, chain-transfer agent and polymerization starter and the total amount of aqueous medium is 56: 44; The amount of the aqueous medium in the initial adding reactor accounts for 74% of aqueous medium total amount; Remain on the boiling temperature (103～105 ℃) of system with temperature of reaction in the dropping process.

After drip finishing, with system temperature with preceding identical temperature under kept 5 minutes obtaining comparison polyacrylic acid (3) thus so that reaction transforms fully.For comparing polyacrylic acid (3), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 2 for it.

(Comparative Example A An-4)

Prepare comparison sodium polyacrylate (4) according to the polyreaction identical, except replacing 482.6 parts of water with 922.7 parts of water when reinforced through ion exchange treatment through ion exchange treatment initial with embodiment A-7.For comparing sodium polyacrylate (4), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 2 for it.

(Comparative Example A An-5)

Prepare comparison sodium polyacrylate (5) according to the polyreaction identical, except replacing 482.6 parts of water with 190.0 parts of water when reinforced through ion exchange treatment through ion exchange treatment initial with embodiment A-7.For comparing sodium polyacrylate (5), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 2 for it.

(Comparative Example A An-6)

At first, 611.5 parts of water through ion exchange treatment are joined in the identical aggregation container that is adopted with embodiment A-1, and under agitation temperature is risen to lentamente the boiling temperature (100 ℃) of system subsequently.

Enter the mouth to wherein dripping following raw materials according respectively by different droppings: 3049.5 part of 37% sodium acrylate aqueous solution and 100.1 part of 15% sodium persulfate aqueous solution, wherein: the dropping time of the 37% sodium acrylate aqueous solution and 15% sodium persulfate aqueous solution was respectively 180 minutes and 185 minutes; The ratio of the total amount of monomer component, chain-transfer agent and polymerization starter and the total amount of aqueous medium is 30: 70; The amount of the aqueous medium in the initial adding reactor accounts for 23% of aqueous medium total amount; Remain on the boiling temperature (100～102 ℃) of system with temperature of reaction in the dropping process.After drip finishing, with system temperature with preceding identical temperature under kept 5 minutes obtaining comparison sodium polyacrylate (6) thus so that reaction transforms fully.For comparing sodium polyacrylate (6), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 2 for it.

(Comparative Example A An-7)

Prepare comparison polyacrylic acid (7) according to the polyreaction identical with embodiment A-1, except replacing 40.1 part of 45% single hydration sodium hypophosphite aqueous solution and when dripping, replace 160.2 part of 45% single hydration sodium hypophosphite aqueous solution with 120.2 part of 45% single hydration sodium hypophosphite aqueous solution when reinforced with 80.1 part of 45% single hydration sodium hypophosphite aqueous solution initial.For comparing polyacrylic acid (7), measure its molecular weight and molecular weight distribution (D value) according to the method identical with embodiment A-1.The results are shown in Table 2 for it.

Table 1

	Preparation condition							Molecular weight and molecular weight distribution
											??(1)	????(2)	????(3)	????(4)	????(5)	??(6)	Type	???Mw	????Mn	??Mw/Mn
	Embodiment A-1	?56∶44	????58	????100	????80	????100	?100～ ??105	Acid type	?6,357	??3,739											??1.70
Embodiment A-2											?56∶44	????55	????100	????100	????100	?100～ ??105	Acid type	?5,234	??2,829	??1.85
	Embodiment A-3	?50∶50	????64	????100	????100	????100	?100～ ??104	Acid type	?5,016	??1,929											??2.60
Embodiment A-4											?47∶53	????68	????100	????100	????100	?100～ ??103	Acid type	?4,934	??1,787	??2.76
	Embodiment A-5	?64∶36	????32	????100	????100	????100	?100～ ??107	Acid type	?6,446	??2,518											??2.56
Embodiment A-6											?56∶44	????55	????100	????100	????100	?100～ ??105	Acid type	?5,316	??2,291	??2.32
	Embodiment A-7	?56∶44	????19	????100	????100	????100	?100～ ??105	The salt type	?5,598	??2,195											??2.55
Embodiment A-8											?56∶44	????57	????100	????95	????100	?100～ ??105	Acid type	?6,516	??3,640	??1.79
	Embodiment A-9	?56∶44	????60	????100	????55	????100	?100～ ??105	Acid type	?6,139	??3,355											??1.83
Embodiment A-10											?56∶44	????59	????100	????100	????100	?100～ ??105	Acid type	?12,156	??4,469	??2.72

(1) amount (weight %) (6) of the polymerization starter that drips of the amount (weight %) (5) of the chain-transfer agent that drips of the amount (weight %) (4) of the monomer component that drips of the amount (weight %) (3) of the aqueous medium of the initial adding of ratio (2) of monomer component, chain-transfer agent and polymerization starter three's total amount and aqueous medium total amount drip and polymerization process in reaction system temperature (℃)

Table 2

	Preparation condition							Molecular weight and molecular weight distribution
											??(1)	????(2)	????(3)	????(4)	????(5)	????(6)	Type	??????Mw	????Mn	??Mw/Mn
	Comparative Example A An-1	?44∶56	????72	????100	????100	????100	????100- ????103	Acid type	?4,837	??1,602											??3.02
Comparative Example A An-2											?56∶44	????64	????100	????0	????100	????100- ????105	Acid type	?8,621	??2,550	??3.38
	Comparative Example A An-3	?56∶44	????74	????60	????40	????70	????100- ????105	Acid type	?12,115	??2,912											??4.16
Comparative Example A An-4											?44∶56	????31	????100	????100	????100	????100- ????105	The salt type	?5,692	??1,830	??3.11
	Comparative Example A An-5	?50∶50	????8	????100	????100	????100	????100- ????106	The salt type	?6,748	??2,032											??3.32
Comparative Example A An-6											?30∶70	????23	????100	????100	????100	????100- ????102	The salt type	?6,191	??2,098	??2.95
	Comparative Example A An-7	?56∶44	????61	????100	????40	????100	????100- ????105	Acid type	?6,442	??2,651											??2.43

(1) amount (weight %) (6) of the polymerization starter that drips of the amount (weight %) (5) of the chain-transfer agent that drips of the amount (weight %) (4) of the monomer component that drips of the amount (weight %) (3) of the aqueous medium of the initial adding of ratio (2) of monomer component, chain-transfer agent and polymerization starter three's total amount and aqueous medium total amount drip and polymerization process in reaction system temperature (℃)

In embodiment A below-11～20 and the Comparative Example A An-8～14, to their the antigelation ability (A) of polymer determination and the sequestering power (B) of gained in embodiment A-1～10 and the Comparative Example A An-1～7.All polymkeric substance all are to measure with the form of its complete neutral salt.The reason of doing like this is not that polymkeric substance only just shows the antigelation ability (A) or the sequestering power (B) of expection under the form of complete neutral salt, but compares in order to be convenient to each other under same active ingredient.

(embodiment A-11)

48% aqueous sodium hydroxide solution is joined in polyacrylic acid (1) (preparing in the embodiment A-1) aqueous solution, regulate its pH value and be 9.0, obtain sodium polyacrylate (1) thus with in fully and polyacrylic acid (1).

The antigelation ability (A) of sodium polyacrylate (1) is 560, and the sequestering power (B) of sodium polyacrylate (1) is 290 milligrams of lime carbonate/grams.In addition, product (A) and (B) is 162400.

(embodiment A-12～16)

Measure antigelation ability (A), sequestering power (B) and (A) and product (B) according to the mode identical, will gather that (methyl) vinylformic acid (2)-(6) (preparing) neutralize fully with sodium hydroxide and poly-(methyl) acrylate (2)～(6) that prepare in embodiment A-2～6 except adopting with embodiment A-11.The results are shown in Table 3 for it.

(embodiment A-17)

Measure antigelation ability (A), sequestering power (B) and (A) and product (B) according to the mode identical, except adopting resulting poly-(methyl) sodium acrylate (7) of embodiment A-7 with embodiment A-11.The results are shown in Table 3 for it.

(embodiment A-18～20)

Measure antigelation ability (A), sequestering power (B) and (A) and product (B) according to the mode identical, will gather that (methyl) vinylformic acid (8)～(10) (preparing) neutralize fully with sodium hydroxide and poly-(methyl) acrylate (8)～(10) that prepare in embodiment A-8～10 except adopting with embodiment A-11.The results are shown in Table 3 for it.

(Comparative Example A An-8～10)

Measure antigelation ability (A), sequestering power (B) and (A) and product (B) according to the mode identical, will gather relatively that (methyl) vinylformic acid (1)～(3) (preparing) neutralize fully with sodium hydroxide and relatively more poly-(methyl) acrylate (1)～(3) that prepare in Comparative Example A An-1～3 except adopting with embodiment A-11.The results are shown in Table 4 for it.

(Comparative Example A An-11～13)

Measure antigelation ability (A), sequestering power (B) and (A) and product (B) according to the mode identical, except adopting resulting relatively more poly-(methyl) sodium acrylate (4)～(6) in Comparative Example A An-4～6 with embodiment A-11.The results are shown in Table 4 for it.

(Comparative Example A An-14)

Measure antigelation ability (A), sequestering power (B) and (A) and product (B) according to the mode identical, will gather relatively that (methyl) vinylformic acid (7) (preparing) neutralizes fully with sodium hydroxide and relatively more poly-(methyl) acrylate (7) of preparing in Comparative Example A An-7 except adopting with embodiment A-11.The results are shown in Table 4 for it.

Table 3

	Poly-(methyl) vinylformic acid (or salt) that adopts	Antigelation ability (A)	Sequestering power (B)	Product (A) * (B)
					Embodiment A-11	The sodium salt completely of embodiment A-1 polymkeric substance	????560	????290	???162,400
Embodiment A-12	The sodium salt completely of embodiment A-2 polymkeric substance	????490	????280	???137,200
					Embodiment A-13	The sodium salt completely of embodiment A-3 polymkeric substance	????220	????270	????59,400
Embodiment A-14	The sodium salt completely of embodiment A-4 polymkeric substance	????130	????260	????33,800
					Embodiment A-15	The sodium salt completely of embodiment A-5 polymkeric substance	????320	????290	????92,800
Embodiment A-16	The sodium salt completely of embodiment A-6 polymkeric substance	????230	????210	????48,300
					Embodiment A-17	The polymkeric substance of embodiment A-7	????160	????240	????38,400
Embodiment A-18	The sodium salt completely of embodiment A-8 polymkeric substance	????520	????290	???150,800
					Embodiment A-19	The sodium salt completely of embodiment A-9 polymkeric substance	????500	????290	???145,000
Embodiment A-20	The sodium salt completely of embodiment A-10 polymkeric substance	????230	????80	????18,400

Table 4

	Poly-(methyl) vinylformic acid (or salt) that adopts	Antigelation ability (A)	Sequestering power (B)	Product (A) * (B)
					Comparative Example A An-8	The sodium salt completely of Comparative Example A An-1 polymkeric substance	????70	????250	?????17,500
Comparative Example A An-9	The sodium salt completely of Comparative Example A An-2 polymkeric substance	????45	????280	?????12,600
					Comparative Example A An-10	The sodium salt completely of Comparative Example A An-3 polymkeric substance	????55	????220	?????12,100
Comparative Example A An-11	The polymkeric substance of Comparative Example A An-4	????65	????240	?????15,600
					Comparative Example A An-12	The polymkeric substance of Comparative Example A An-5	????32	????290	??????9,280
Comparative Example A An-13	The polymkeric substance of Comparative Example A An-6	????66	????210	?????13,860
					Comparative Example A An-14	The sodium salt completely of Comparative Example A An-7 polymkeric substance	????74	????230	?????17,020

In Embodiment B below-1～14 and the Comparative Examples B-1～8, estimate the inhibition recontaminate ability of the polymkeric substance of embodiment A-1～10 and Comparative Example A An-1～7 gained.As previously mentioned, for the polymkeric substance of embodiment A-1～10 gained, their purposes as detergent builder is included among the compound experiment embodiment of the present invention.But for the polymkeric substance of Comparative Example A An-1～7 gained, even their purposes as detergent builder all is not included among the present invention.

(Embodiment B-1)

The inhibition recontaminate ability of the sodium polyacrylate (1) that is obtained by neutralizing fully of polyacrylic acid (1) (being prepared by embodiment A-1) is measured according to the methods below:

＜inhibition recontaminate ability 〉

At first prepare following solution:

(a) hard water: will join through the water of ion exchange treatment in 1.47 grams, the two hydration calcium chloride, and the adjusting total amount is that 5000 grams obtain solution (concentration that this solution contains the calcium ion of calcium carbonate form is 200ppm);

(b) 5% aqueous sodium carbonate;

(c) 5%LAS (sodium salt of the linear chain alkyl benzene sulphonate (ABS)) aqueous solution;

(d) 1% sodium polyacrylate (1) aqueous solution.

One liter of solution (a) and 1 gram clay (JIS test powder #1.7) are joined in the Terg-O-Tometer jar (temperature regulation to 25 ℃) and stirred 1 minute with 100 rev/mins speed subsequently.

Then to wherein adding a white cotton (5 centimetres of 5 cm x), and stirred immediately 1 minute.Afterwards, add 4 gram solution (b), 4 gram solution (c), 0.15 gram zeolite A4 powder and 5 gram solution (d), and under 100 rev/mins speed, the gained mixture was stirred 10 minutes subsequently, the total amount that wherein contains the auxiliary agent of zeolite and sodium polyacrylate (1) is 0.20 part, with for per 100 parts of zeolites, the amount of the sodium polyacrylate that is added (1) is 33.3 parts.After stirring end the water on the white cotton is wrung out, and removed the clay that adsorbs in the jar.Then, be during 25 ℃ water adds jar with 1 intensification degree, and add above-mentioned white cotton subsequently, under 100 rev/mins speed, stir rinsing 2 minutes then.This rinse cycle carries out twice.

With the aforesaid operations triplicate,, meanwhile its gauffer is flattened with an iron then with white cotton drying.Whiteness (1) with the dry white cotton of a colorimeter measurement.In addition, also measure the whiteness (2) of not test (N.T.) white cotton with colour-difference meter.Calculate reduction value (2)-(1) of whiteness thus.Carry out aforesaid operations with 10 white cottons, and calculate average whiteness reduction value (I).In addition do not have solution (d) in the presence of carry out same operation to calculate average whiteness reduction value (II) as blank.Calculate the recontaminate ability that suppresses according to following equation.The results are shown in Table 5 for it.

Suppress recontaminate ability=((II)-(I))/(II) * 100

(Embodiment B-2)

Calculate inhibition recontaminate ability according to the mode identical, except replacing zeolite with tripoly phosphate sodium STPP (STPP) with Embodiment B-1.The results are shown in Table 5 for it.

(Embodiment B-3)

Calculate the recontaminate ability that suppresses according to the mode identical with Embodiment B-1, except with adopt sodium hydroxide fully in and polyacrylic acid (2) (preparing) and the sodium polyacrylate (2) for preparing replaces sodium polyacrylate (1) by embodiment A-2.The results are shown in Table 5 for it.

(Embodiment B-4)

Calculate inhibition recontaminate ability according to the mode identical, except replacing zeolite with tripoly phosphate sodium STPP (STPP) with Embodiment B-3.The results are shown in Table 5 for it.

(Embodiment B-5～6)

Calculate the recontaminate ability that suppresses according to the mode identical, except the zeolite that adopted and the ratio of sodium polyacrylate (2) are the numerical value shown in the table 5 with Embodiment B-3.The results are shown in Table 5 for it.

(Embodiment B-7～10)

Calculate the recontaminate ability that suppresses according to the mode identical, except poly-(methyl) acrylate (3)～(6) of preparation replace sodium polyacrylate (1) with adopting sodium hydroxide to neutralize poly-(methyl) vinylformic acid (3)～(6) (being prepared by embodiment A-3～6) fully with Embodiment B-1.The results are shown in Table 5 for it.

(Embodiment B-11)

Calculate the recontaminate ability that suppresses according to the mode identical, except poly-(methyl) sodium acrylate (7) for preparing with embodiment A-7 replaces sodium polyacrylate (1) with Embodiment B-1.The results are shown in Table 5 for it.

(Embodiment B-12～14)

Calculate the recontaminate ability that suppresses according to the mode identical, except poly-(methyl) acrylate (8)～(10) of preparation replace sodium polyacrylate (1) with adopting sodium hydroxide to neutralize poly-(methyl) vinylformic acid (8)～(10) (being prepared by embodiment A-8～10) fully with Embodiment B-1.The results are shown in Table 5 for it.

(Comparative Examples B-1～3)

Calculate the recontaminate ability that suppresses according to the mode identical, except relatively more poly-(methyl) acrylate (1)～(3) of preparation replace sodium polyacrylate (1) with adopting poly-(methyl) vinylformic acid (1)～(3) (being prepared by Comparative Example A An-1～3) of the complete neutralization ratio of sodium hydroxide with Embodiment B-1.The results are shown in Table 6 for it.

(Comparative Examples B-4～6)

Calculate the recontaminate ability that suppresses according to the mode identical, replace sodium polyacrylate (1) except using relatively more poly-(methyl) sodium acrylate (4)～(6) that prepare by Comparative Example A An-4～6 with Embodiment B-1.The results are shown in Table 6 for it.

(Comparative Examples B-7)

Calculate the recontaminate ability that suppresses according to the mode identical, except relatively more poly-(methyl) acrylate (7) of preparation replaces sodium polyacrylate (1) with adopting poly-(methyl) vinylformic acid (7) (being prepared by Comparative Example A An-7) of the complete neutralization ratio of sodium hydroxide with Embodiment B-1.The results are shown in Table 6 for it.

(Comparative Examples B-8)

Calculate inhibition recontaminate ability according to the mode identical, except only adopting 0.2 part of zeolite as auxiliary agent with Embodiment B-1.The results are shown in Table 6 for it.

Table 5

	Inorganic assistant agent (1)		Poly-(methyl) acrylate (2)		??(1)/(2)	Suppress the recontaminate ability
							Kind	Addition (part)	Kind	Addition (part)
	Embodiment B-1	Zeolite	????0.15	The complete sodium salt of embodiment A-1 polymkeric substance							????0.05	?100/33.3	????87
Embodiment B-2					?STPP	????0.15	The complete sodium salt of embodiment A-1 polymkeric substance	????0.05	?100/33.3	????89
	Embodiment B-3	Zeolite	????0.15	The complete sodium salt of embodiment A-2 polymkeric substance							????0.05	?100/33.3	????85
Embodiment B-4					?STPP	????0.15	The complete sodium salt of embodiment A-2 polymkeric substance	????0.05	?100/33.3	????87
	Embodiment B-5	Zeolite	????0.198	The complete sodium salt of embodiment A-2 polymkeric substance							????0.002	?100/1.0	????64
Embodiment B-6					Zeolite	????0.019	The complete sodium salt of embodiment A-2 polymkeric substance	????0.181	?100/953	????88
	Embodiment B-7	Zeolite	????0.15	The complete sodium salt of embodiment A-3 polymkeric substance							????0.05	?100/33.3	????74
Embodiment B-8					Zeolite	????0.15	The complete sodium salt of embodiment A-4 polymkeric substance	????0.05	?100/33.3	????68
	Embodiment B-9	Zeolite	????0.15	The complete sodium salt of embodiment A-5 polymkeric substance							????0.05	?100/33.3	????79
Embodiment B-10					Zeolite	????0.15	The complete sodium salt of embodiment A-6 polymkeric substance	????0.05	?100/33.3	????82
	Embodiment B-11	Zeolite	????0.15	The polymkeric substance of embodiment A-7							????0.05	?100/33.3	????77
Embodiment B-12					Zeolite	????0.15	The complete sodium salt of embodiment A-8 polymkeric substance	????0.05	?100/33.3	????86

Embodiment B-13	Zeolite	????0.15	The complete sodium salt of embodiment A-9 polymkeric substance	????0.05	??100/33.3	????85
							Embodiment B-14	Zeolite	????0.15	The complete sodium salt of embodiment A-10 polymkeric substance	????0.05	??100/33.3	????66

Table 6

	Inorganic assistant agent (1)		Relatively more poly-(methyl) acrylate (3)		???(1)/(3)	Suppress the recontaminate ability
							Kind	Addition (part)	Kind	Addition (part)
	Comparative Examples B-1	Zeolite	????0.15	The complete sodium salt of Comparative Example A An-1 polymkeric substance							????0.05	?100/33.3	????56
Comparative Examples B-2					Zeolite	????0.15	The complete sodium salt of Comparative Example A An-2 polymkeric substance	????0.05	?100/33.3	????52
	Comparative Examples B-3	Zeolite	????0.15	The complete sodium salt of Comparative Example A An-3 polymkeric substance							????0.05	?100/33.3	????22
Comparative Examples B-4					Zeolite	????0.15	The polymkeric substance of Comparative Example A An-4	????0.05	?100/33.3	????45
	Comparative Examples B-5	Zeolite	????0.15	The polymkeric substance of Comparative Example A An-5							????0.05	?100/33.3	????37
Comparative Examples B-6					Zeolite	????0.15	The polymkeric substance of Comparative Example A An-6	????0.05	?100/33.3	????33
	Comparative Examples B-7	Zeolite	????0.15	The complete sodium salt of Comparative Example A An-7 polymkeric substance							????0.05	?100/33.3	????55
Comparative Examples B-8					Zeolite	????0.20	Do not add	????0	????100/0	????5

In Embodiment C below-1～3 and comparing embodiment C-1～14, estimate the mineral dye dispersive ability of the polymkeric substance of embodiment A-1～10 and Comparative Example A An-1～7 gained.As previously mentioned, for the embodiment A in the embodiment A-1～10-1,8 and 9,1～50% chain-transfer agent is joined in the reactor in advance, remainder adds gradually then, so resulting polymers is included among the compound experiment embodiment of the present invention as the mineral dye dispersion agent or as the purposes of Scale inhibitors.For the embodiment except that embodiment A-1,8 and 9 in the embodiment A series, 100% chain-transfer agent is added gradually, so resulting polymers does not comprise in the present invention as the purposes of mineral dye dispersion agent or as the purposes of Scale inhibitors.For the polymkeric substance of Comparative Example A An-1～7 gained, they all be not included among the present invention as the purposes of mineral dye dispersion agent or as the purposes of Scale inhibitors.

(Embodiment C-1)

To be neutralized to the pH value fully by the polyacrylic acid (1) that embodiment A-1 prepares with sodium hydroxide is 9.0.The neutralized reaction product that obtains for planting mode is thus measured its mineral dye dispersive ability and scale inhibition ability according to the methods below.The results are shown in Table 7.

＜mineral dye dispersive ability 〉

At first, with poly-(methyl) acrylate polymer of 0.6 gram, 128.0 grams are through the water and 300 gram lime carbonate (mineral dye, the Super#200 of ion exchange treatment, Maruo Calcium company produces) to join a volume be in 450 milliliters the mayonnaise bottle, and stir with a spatula subsequently.Then, with 150 gram diameters is that 3.5 millimeters granulated glass sphere joins in the mayonnaise bottle, its contained material carries out jolting with a paint mixer subsequently to be mixed 30 minutes, so that lime carbonate disperses in the deionized water, the aqueous dispersion that obtains thus is called as slurries, and the concentration of its lime carbonate is 70% (weight).After preparation, use its viscosity of Type B rotary viscosity design determining immediately and after through 50 ℃ * 30 days, measure its viscosity.

＜scale inhibition ability 〉

At first, it is in 225 milliliters the vial, subsequently to wherein sneaking into 10 gram 1.56% (weight) the two hydration calcium chloride waters and poly-(methyl) acrylate polymer aqueous solution of 1 gram, 0.02% (weight) that 175 grams are joined a volume through the water of ion exchange treatment.Further, to wherein adding 10 gram 3% (weight) sodium bicarbonate aqueous solutions and mixing, obtain the supersaturated aqueous solution that lime carbonate concentration is 530ppm thus.This supersaturated aqueous solution sealing was also heated 5 hours down at 75 ℃ subsequently.Filter with 0.45 micron membranes strainer after the cooling, and analyze calcium hardness in the gained filtrate according to JIS K0101 standard method.Calculate the inhibiting rate (%) of lime scale according to following calculating formula by the result of gained, estimate the inhibition ability of lime scale thus.

The inhibiting rate of lime scale (%)=(C-B)/(A-B) * 100

Wherein:

A be before 75 ℃ of thermal treatments 5 hours lime carbonate concentration (=530ppm);

B is under the situation of poly-(methyl) acrylate polymer aqueous solution of unmixed 0.02% (weight), the concentration of lime carbonate in the filtrate; With

C is under the situation that is mixed with poly-(methyl) acrylate polymer aqueous solution of 0.02% (weight), the concentration of lime carbonate in the filtrate.

(Embodiment C-2～3)

Poly-(methyl) acrylate copolymer (8)～(9) embodiment A-8～9 is prepared with sodium hydroxide neutralize, so that its pH value is 9.0.For the neutralized reaction product that mode thus obtains, estimate its mineral dye dispersive ability and scale inhibition ability according to aforesaid mode.The results are shown in Table 7.

(comparing embodiment C-1～5)

Poly-(methyl) acrylate copolymer (2)～(6) embodiment A-2～6 is prepared with sodium hydroxide neutralize, so that its pH value is 9.0.For the neutralized reaction product that mode thus obtains, estimate its mineral dye dispersive ability and scale inhibition ability according to aforesaid mode.The results are shown in Table 8.

(comparing embodiment C-6)

Estimate mineral dye dispersive ability and scale inhibition ability according to the mode identical, except adopting by the prepared sodium polyacrylate of embodiment A-7 (7) with Embodiment C-1.The results are shown in Table 8.

(comparing embodiment C-7)

Poly-(methyl) acrylate copolymer (10) embodiment A-10 is prepared with sodium hydroxide neutralizes, so that its pH value is 9.0.For the neutralized reaction product that mode thus obtains, estimate its mineral dye dispersive ability and scale inhibition ability according to aforesaid mode.The results are shown in Table 8.

(comparing embodiment C-8～10)

Relatively more poly-(methyl) acrylate copolymer (1)～(3) Comparative Example A An-1～3 is prepared with sodium hydroxide neutralize, so that its pH value is 9.0.For the neutralized reaction product that mode thus obtains, estimate its mineral dye dispersive ability and scale inhibition ability according to aforesaid mode.The results are shown in Table 8.

(comparing embodiment C-11～13)

Estimate mineral dye dispersive ability and scale inhibition ability according to the mode identical, except adopting by prepared comparison sodium polyacrylate (4)～(6) of Comparative Example A An-4～6 with Embodiment C-1.The results are shown in Table 8.

(comparing embodiment C-14)

Poly-(methyl) acrylate copolymer (7) Comparative Example A An-7 is prepared with sodium hydroxide neutralizes so that its pH value is 9.0.For the neutralized reaction product that mode thus obtains, estimate its mineral dye dispersive ability and scale inhibition ability according to aforesaid mode.The results are shown in Table 8.

Table 7

	Poly-(methyl) vinylformic acid (or salt) that adopts	The viscosity of 70% calcium carbonate water dispersion (CP)		Incrustation scale inhibiting rate (%)
					After the preparation	After 50 ℃ * 30 days
		Embodiment C-1	The complete sodium salt of embodiment A-1 polymkeric substance				????210	????220	????74
Embodiment C-2	The complete sodium salt of embodiment A-8 polymkeric substance			????230	????240	????73
		Embodiment C-3	The complete sodium salt of embodiment A-9 polymkeric substance				????270	????300	????71

Table 8

	Poly-(methyl) vinylformic acid (or salt) that adopts	The viscosity of 70% calcium carbonate water dispersion (CP)		Incrustation scale inhibiting rate (%)
					After the preparation	After 50 ℃ * 30 days
		Comparing embodiment C-1	The complete sodium salt of embodiment A-2 polymkeric substance				????300	????360	????68
Comparing embodiment C-2	The complete sodium salt of embodiment A-3 polymkeric substance			????310	????360	????65
		Comparing embodiment C-3	The complete sodium salt of embodiment A-4 polymkeric substance				????320	????340	????67
Comparing embodiment C-4	The complete sodium salt of embodiment A-5 polymkeric substance			????290	????330	????63
		Comparing embodiment C-5	The complete sodium salt of embodiment A-6 polymkeric substance				????340	????370	????25
Comparing embodiment C-6	The polymkeric substance of embodiment A-7			????300	????330	????64
		Comparing embodiment C-7	The complete sodium salt of embodiment A-10 polymkeric substance				????330	????410	????51
Comparing embodiment C-8	The complete sodium salt of Comparative Example A An-1 polymkeric substance			????470	????580	????43
		Comparing embodiment C-9	The complete sodium salt of Comparative Example A An-2 polymkeric substance				????650	????810	????40
Comparing embodiment C-10	The complete sodium salt of Comparative Example A An-3 polymkeric substance			????840	????1130	????33
		Comparing embodiment C-11	The polymkeric substance of Comparative Example A An-4				????640	????950	????36
Comparing embodiment C-12	The polymkeric substance of Comparative Example A An-5			????770	????1260	????37
		Comparing embodiment C-13	The polymkeric substance of Comparative Example A An-6				????1280	????1700	????25
Comparing embodiment C-14	The complete sodium salt of Comparative Example A An-7 polymkeric substance			????510	????630	????48

Can carry out change on the various details to the present invention under the situation that does not deviate from theme of the present invention and scope.Further, the foregoing description of the preferred embodiment of the invention just is used for illustrating the present invention, they should not be counted as by attached claim and their determined theme of the present invention of Equivalent and scope any restriction being arranged.

Claims (11)

1, a kind of detergent builder, (A * B) is more than or equal to poly-(methyl) vinylformic acid (or salt) polymkeric substance of 18000 to contain the product of antigelation ability (A) and sequestering power (B).

2, according to the detergent builder of claim 1, wherein the weight-average molecular weight of poly-(methyl) vinylformic acid (or salt) polymkeric substance and the ratio of number-average molecular weight are 1.5～2.8.

3, according to the detergent builder of claim 1 or 2, wherein poly-(methyl) vinylformic acid (or salt) polymkeric substance prepares by containing more than or equal to the monomeric monomer component of 90% (weight) (methyl) vinylformic acid (or salt), and its weight-average molecular weight is 1000～100000.

4, according to each detergent builder of claim 1 to 3, wherein poly-(methyl) vinylformic acid (or salt) polymkeric substance contains the P atom in its molecule.

5, a kind of preparation method of detergent builder, comprise with most of component for the monomer component of (methyl) vinylformic acid (or salt) in the presence of chain-transfer agent and polymerization starter in aqueous medium step of polymerization, obtain containing the detergent builder of poly-(methyl) vinylformic acid (or salt) polymkeric substance of gained thus;

The method is characterized in that:

The ratio of monomer component, chain-transfer agent and polymerization starter three's the gross weight and the gross weight of aqueous medium is 46: 54 to 66: 34;

Chain-transfer agent more than or equal to 0～50% (weight) of the aqueous medium of 10% (weight) of aqueous medium total amount and chain-transfer agent total amount joins in the reactor in advance; With

Polymerization is to carry out under 50～120 ℃ in temperature of reaction, in this process more than or equal to the monomer component of 70% (weight) of monomer component total amount, more than or equal to the chain-transfer agent of 50% (weight) of chain-transfer agent total amount with little by little to join temperature more than or equal to the polymerization starter of 80% (weight) of polymerization starter total amount be in 50～120 ℃ the reaction system.

6, according to the preparation method of claim 5, wherein most of component of monomer component is (methyl) vinylformic acid, and this method further comprises to be used in the alkaline reagents after polymerization and the step of resulting polymers, is gathered (methyl) acrylate thus.

7,, contain 1～1000 part (weight) poly-(methyl) vinylformic acid (or salt) polymkeric substance and 100 parts of (weight) inorganic assistant agents according to each detergent builder of claim 1～4.

8, a kind of poly-(methyl) vinylformic acid (or salt) polymkeric substance, it be by be included in most of component for the monomer component of (methyl) vinylformic acid (or salt) in the presence of chain-transfer agent and polymerization starter in aqueous medium the method for step of polymerization prepare;

This polymkeric substance is characterised in that:

The ratio of monomer component, chain-transfer agent and polymerization starter three's the gross weight and the gross weight of aqueous medium is 46: 54 to 66: 34;

Chain-transfer agent more than or equal to 1～50% (weight) of the aqueous medium of 10% (weight) of aqueous medium total amount and chain-transfer agent total amount joins in the reactor in advance; With

Polymerization is to carry out under 50～120 ℃ in temperature of reaction, in this process more than or equal to the monomer component of 70% (weight) of monomer component total amount, more than or equal to the chain-transfer agent of 50% (weight) of chain-transfer agent total amount with little by little to join temperature more than or equal to the polymerization starter of 80% (weight) of polymerization starter total amount be in 50～120 ℃ the reaction system.

9, poly-(methyl) vinylformic acid (or salt) polymkeric substance according to Claim 8, the product of its antigelation ability (A) and sequestering power (B) (A * B) more than or equal to 18000 and the ratio of weight-average molecular weight and number-average molecular weight be 1.5～2.8.

10, a kind of mineral dye dispersion agent contains claim 8 or 9 desired poly-(methyl) vinylformic acid (or salt) polymkeric substance.

11, a kind of Scale inhibitors contains claim 8 or 9 desired poly-(methyl) vinylformic acid (or salt) polymkeric substance.